EP2573047B1 - Method for producing onion-like carbon - Google Patents

Method for producing onion-like carbon Download PDF

Info

Publication number
EP2573047B1
EP2573047B1 EP11867256.7A EP11867256A EP2573047B1 EP 2573047 B1 EP2573047 B1 EP 2573047B1 EP 11867256 A EP11867256 A EP 11867256A EP 2573047 B1 EP2573047 B1 EP 2573047B1
Authority
EP
European Patent Office
Prior art keywords
vacuum tank
gas
carbon
diamond
container
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP11867256.7A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP2573047A4 (en
EP2573047A1 (en
Inventor
Nobuo Ohmae
Nobuyuki TERAYAMA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ohmae Nobuo
Shinko Seiki Co Ltd
Original Assignee
Ohmae Nobuo
Shinko Seiki Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ohmae Nobuo, Shinko Seiki Co Ltd filed Critical Ohmae Nobuo
Publication of EP2573047A1 publication Critical patent/EP2573047A1/en
Publication of EP2573047A4 publication Critical patent/EP2573047A4/en
Application granted granted Critical
Publication of EP2573047B1 publication Critical patent/EP2573047B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/18—Nanoonions; Nanoscrolls; Nanohorns; Nanocones; Nanowalls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/773—Nanoparticle, i.e. structure having three dimensions of 100 nm or less

Definitions

  • This invention relates to a method and system for manufacturing onion-like carbon (hereinafter referred to as OLC).
  • OLC is in the form of spherical particles having a diameter of from several nanometers to several tens of nanometers, exhibit a significantly low coefficient of friction both in air and in a vacuum and have good bearing resistance, they are expected to find applications as solid-state lubricants in particular.
  • An example of methods for manufacturing such OLC is disclosed in, for example, Patent Literature 1.
  • diamond nanopowder hereinafter referred to as DNP
  • This DNP is then hot-processed in an inert gas atmosphere at a temperature of from 1,600 °C to 1,800 °C, which results in OLC.
  • Patent Literature 1 JP 11-157818A
  • the starting material ODN is expensive (i.e. around ⁇ 5,000/g)
  • the end product OLC is also expensive.
  • the above-described prior technology has a problem in its cost.
  • WO2011/004609 which is considered to represent the closest prior art, discloses a device which uses CO2 in exhaust gasses as a carbon source and immobilises the carbon in the CO2 to create an advanced carbon fuel in the form of useful, high added value nanocarbon structures such as multi-layer carbon-nano tubes, carbon-onions or the like, and which also reduces the quantity of the CO2 contained in exhaust gasses that is omitted into the atmosphere.
  • an object of the present invention is to provide a method and a system for manufacturing OLC at a lower cost.
  • the present invention there is provided a method of manufacturing onion-like carbon with hydrocarbon gas used as a starter material according to claim 1.
  • the present invention further provides an onion-like carbon manufacturing system for manufacturing onion-like carbon using hydrocarbon gas as a starter material as defined in claim 6.
  • OLC is manufactured (or synthesized) with a hydrocarbon gas used as a starting material. More specifically, in the DLC powder producing step, DLC powder, which is hard carbon powder, is produced by plasma CVD in which a hydrocarbon gas is used as a material gas. In the converting step, the DLC powder is heated in a vacuum or in an inert gas atmosphere, whereby the DLC powder is converted to OLC. In this manner, OLC is manufactured.
  • the useable hydrocarbon gases include acetylene (C 2 H 2 ) gas, methane (CH 4 ) gas, ethylene (C 2 H 4 ) gas, benzene (C 6 H 6 ) gas etc., but, from a comprehensive viewpoint, with the DLC powder producing efficiency and cost, easiness of handling, easiness of procurement and safety of the material gas, etc. taken into consideration, acetylene gas is suitable.
  • the DLC powder producing step includes a plasma generating step, a gas introducing step and a temperature controlling step, which are described below.
  • the plasma generating step AC discharging power is supplied to a vacuum tank connected to a reference potential and to an open-mouthed container disposed in the vacuum tank, using the tank and the container as a pair of electrodes. This causes plasma to be generated in the vacuum tank with the container disposed therein.
  • the gas introducing step a hydrocarbon gas is introduced into the vacuum tank. The hydrocarbon gas is decomposed (dissociated) by the plasma, which causes DLC powder to be formed over the surfaces of the container, and over the inner wall of the container in particular.
  • the temperature controlling step is employed in which the temperature within the container is controlled not to rise above 300 °C.
  • the hydrocarbon gas in the gas introducing step, it is preferable for the hydrocarbon gas to be introduced into the vacuum tank through a gas introducing pipe insulated from the vacuum tank, with the hydrocarbon gas outlet port of the gas introducing pipe disposed preferably near the mouth of the container.
  • This arrangement makes it possible for the hydrocarbon gas to be directly introduced into the container, resulting in improvement of the efficiency of production of the DLC powder on the inner wall of the container.
  • the DLC powder producing step to include a DC power supplying step in which DC power of positive potential referenced to the reference potential is supplied to the gas introducing pipe.
  • the gas introducing pipe functions as an anode electrode, whereby electrons in the plasma are attracted into the gas introducing pipe.
  • high-density discharge or what is called hollow-anode discharge is formed around the gas introducing pipe, or near the hydrocarbon gas outlet port of the gas introducing pipe in particular.
  • the formation of the hollow-anode discharge improves the hydrocarbon gas decomposition efficiency, leading to further improvement of the efficiency of production of the DLC powder over the inner wall of the container.
  • the DC power supplying steps also contributes to the stabilization of the plasma.
  • the plasma is generated by the application of AC discharging power, using the vacuum tank and the container as a pair of electrodes.
  • DLC powder adheres not only to the surface (inner wall) of the container but also to the surface (inner wall) of the vacuum tank.
  • the function of the vacuum tank as an electrode is degraded, leading to instability of the plasma.
  • the DLC powder producing step may include a magnetic field forming step for forming a magnetic field in the vacuum tank to confine the plasma within the container.
  • the employment of the magnetic field forming step increases the plasma density in the container, leading to further improvement of the efficiency of producing DLC powder adhering to the inner wall of the container.
  • the converting step may include a conversion environment forming step for evacuating the vacuum tank or placing the vacuum tank in an inert gas atmosphere, and a heating step for heating the DLC powder at a temperature of from 700 °C to 2,000 °C in the vacuum tank which has evacuated or placed in the inert gas atmosphere.
  • a conversion environment forming step for evacuating the vacuum tank or placing the vacuum tank in an inert gas atmosphere
  • a heating step for heating the DLC powder at a temperature of from 700 °C to 2,000 °C in the vacuum tank which has evacuated or placed in the inert gas atmosphere.
  • the DLC powder may be heated in the above-described container, or after being transferred to another container. It should be noted here that, if oxygen is present in the vacuum tank when the DLC powder is heated, for example, the DLC powder is oxidized or, in other words, gasified into carbon oxide (CO), carbon dioxide (CO 2 ), or the like. To avoid this inconvenience, the conversion environment forming step is carried out prior to the heating step to evacuate the vacuum tank or place it in an inert gas atmosphere.
  • Acetylene gas is the most suitable as the hydrocarbon gas.
  • the specific structure of the system of the invention includes a vacuum tank connected to a reference potential and an open-mouthed container disposed within the vacuum tank.
  • the DLC powder producing means of such specific structure includes plasma generating means, gas introducing means and temperature control means, which are described hereinafter.
  • the plasma generating means generates plasma in the vacuum tank with the container disposed therein, by applying AC discharging power to the vacuum tank and the container used a pair of electrodes.
  • the gas introducing means introduces the hydrocarbon gas into the vacuum tank.
  • the temperature control means controls the temperature in the container so that it does not rise above 300 °C.
  • the gas introducing means may include a gas introducing pipe which is insulated from the vacuum tank.
  • the hydrocarbon gas is introduced into the vacuum tank through the gas introducing pipe.
  • the gas introducing pipe has its hydrocarbon gas outlet port, from which the hydrocarbon gas is introduced into the vacuum tank, disposed near the mouth of the container.
  • the DLC powder producing means may include DC power supplying means for supplying the gas introducing pipe with DC power at a positive potential referenced to reference potential.
  • the DLC powder producing means may include magnetic field forming means for forming a magnetic field in the vacuum tank to confine the plasma within the container.
  • the converting means may include conversion environment forming means to evacuate the vacuum tank or place the vacuum tank in an inert gas atmosphere, and heating means heating the DLC powder in the vacuum tank which has been evacuated or placed in an inert gas atmosphere, at a temperature of from 700 °C to 2,000 °C.
  • an OLC manufacturing system 10 includes a generally cylindrical vacuum tank 12 having its two ends closed.
  • the vacuum tank 12 is disposed with its one end portion being a top wall and with the other end being a bottom wall.
  • the diameter of the inner space of the vacuum tank 12 is about 1,100 mm, and the height is about 1,000 mm.
  • the shape and dimensions of the vacuum tank 12 are only an example, and can be appropriately determined.
  • the vacuum tank 12 is made of a metal, e.g. SUS 304 stainless steel, having high corrosion resistance and high heat resistance.
  • the wall of the vacuum tank 12 is connected to the ground potential which serves as a reference potential.
  • An exhaust port 14 is formed in the vacuum tank 12 at an appropriate portion in the wall, e.g. at a position slightly outward (leftward in Figure 1 ) of the center of the bottom wall.
  • a vacuum pump (not shown) disposed external to the vacuum tank 12 is connected to the exhaust port 14 through an exhaust pipe (not shown).
  • the vacuum pump serves as exhausting means.
  • the vacuum pump further serves as pressure control means for controlling the pressure P within the vacuum tank 12.
  • a valve (not shown) is disposed in the exhaust pipe, and functions as pressure control means, too.
  • a container or crucible 16 is disposed.
  • the crucible 16 is generally cylindrical in shape, with one end open-mouthed and with the other end closed, and disposed with the open-mouthed end facing upward.
  • the crucible 16 has an outer diameter of about 300 mm, and a height of about 300 mm, and the thicknesses of the side and bottom walls thereof are both about 1 mm (or several millimeters).
  • the material of the crucible 16 is a high melting point material, which is also electrically conductive and non-magnetic, and exhibits low adherence to later-mentioned OLC powder 100.
  • An example of the material of the crucible 16 is molybdenum (Mo).
  • the material for the crucible 16 is not limited to molybdenum, and other high melting point material, such as tantalum (Ta), tungsten (W), and graphite (C), can be used.
  • the shape and dimensions of the crucible 16 can be appropriately determined.
  • the shape in particular, is not limited to a generally cylindrical shape, but other open-mouthed crucible, such as a rectangular shaped crucible and a dish shape crucible, may be used.
  • Asymmetrical pulse discharging power Ep is supplied to the crucible 16 from a pulse power supply 18 disposed external to the vacuum tank 12.
  • the pulse power supply 18 acts as discharging power supplying means.
  • the asymmetrical pulse power Ep is applied between the vacuum tank 12 acting as an anode electrode and the crucible 16 acting as a cathode electrode.
  • the voltage of the asymmetrical pulse power Ep has a rectangular waveform having a higher level voltage value fixed to +37 V and having a lower level voltage value of equal to or more negative than -37 V.
  • the frequency of this voltage can be adjusted as desired within a range of from 10 KHz to 500 KHz through the pulse power supply 18.
  • the duty ratio and the lower level voltage value of this rectangular voltage can be adjusted as desired through the pulse power supply 18.
  • the average voltage value (converted DC value) Vp of the rectangular voltage can be adjusted as desired to a value within a range of from 0 V to -1,000 V.
  • a generally cylindrical heater 20 of a size slightly larger than the crucible 16 is disposed around the (side and bottom walls of) crucible 16.
  • the heater 20 is heated when heater energizing power is supplied thereto from a heater power supply (not shown) disposed external to the vacuum tank 12.
  • the heater 20 controllably heats the crucible 16, or more specifically the inner wall of the crucible 16, to a desired temperature within a range of from 100 °C to 2,000 °C.
  • a gas introducing pipe 22 extends through an appropriate portion of the wall, e.g. the top wall, of the vacuum tank 12.
  • the gas introducing pipe 22 is made of a high melting point metal, such as molybdenum and tantalum, and is insulated from the vacuum tank 12 by means of an insulator 24.
  • the tip end, or more specifically, the inner end in the vacuum tank 12, of the gas introducing pipe 22 is located substantially at the center of the mouth of the crucible 16.
  • the proximal end of the gas introducing pipe 22 is coupled to a discharge gas supplying source, e.g. an argon (Ar) gas supplying source (not shown) and to a material gas supplying source, e.g.
  • an acetylene gas supplying source (not shown), which are disposed external to the vacuum tank 12.
  • Mass flow controllers (not shown) serving as flow rate controlling means for individually controlling the flow rates of the argon and acetylene gases flowing through the gas introducing pipe 22, and on-off valves (not shown) serving as on-off means for individually turning on and off the flows of the argon and acetylene gases, are provided at locations on the gas introducing pipe 22 outside the vacuum tank 12.
  • DC power Ea at a positive potential referenced to ground potential is coupled to a nozzle power supply device 26 serving as DC power supply means disposed outside the vacuum tank 12.
  • the voltage value Va of the DC power Ea can be adjusted through the nozzle power supply device 26 to a desired value within a range of from, for example, +10 V to +100 V.
  • a pair of electromagnetic coils 28 and 30 serving as magnetic field forming means are disposed to extend respectively along the peripheries of the top and bottom walls of the vacuum tank 12.
  • the electromagnetic coils 28 and 30 are supplied with DC magnetic field forming power from a magnetic field forming power supply (not shown) disposed external to the vacuum tank 12, to thereby form what is called a mirror magnetic field in the vacuum tank 12 for confining later-mentioned plasma 200 in the central part of the vacuum tank 12 or, preferably, confine the plasma within the crucible 16.
  • the intensity of the mirror magnetic field is adjustable so as to realize a value within a range of from 1 mT to 10 mT within the crucible 16.
  • OLC can be manufactured, using acetylene as a starting material.
  • DLC powder producing processing is carried out as the first step.
  • DLC powder 100 is produced by plasma CVD, using acetylene gas as a material gas.
  • DLC-to-OLC converting processing is performed as a second step.
  • the DLC powder 100 produced in the preceding DLC powder producing processing is heated in an argon gas atmosphere by means of the heater 20. The heating causes the DLC powder to be converted to OLC. In this manner, OLC is completed.
  • evacuation is performed as a pretreatment
  • the second, converting processing step post-treatment for taking the ultimately manufactured OLC out of the vacuum tank 12 is performed.
  • the vacuum tank 12 is exhausted of air by the vacuum pump until the pressure P within the vacuum tank 12 becomes 2 x 10 -3 Pa or lower, preferably, 5 x 10 -4 Pa or lower.
  • the DLC producing processing as the first step is carried out.
  • Argon gas is introduced into the vacuum tank 12 through the gas introducing pipe 22.
  • the asymmetrical pulse power Ep is applied from the pulse power supply 18, using the vacuum tank 12 as an anode electrode and using the crucible 16 as a cathode electrode. This causes a discharge to be generated in the argon gas in the vacuum tank 12, whereby plasma 200 is generated in the vacuum tank 12.
  • acetylene gas is introduced into the vacuum tank 12 through the gas introducing pipe 22. The acetylene gas is then decomposed by the plasma 200, resulting in production of carbon ions, or decomposition particles of the acetylene gas.
  • the production of DLC powder 100 is considered to be a result of simultaneous occurrence of the following two processes.
  • One is formation of a coating of DLC on the inner wall surface of the crucible 16, which coating peels off from the inner wall of the crucible 16 due to its own internal stress, resulting in the production of the DLC powder 100.
  • the other is a result of recombination in a gaseous phase of the carbon radicals and carbon ions which are particles resulting from the decomposition of acetylene gas caused by the plasma 200. This results in the deposition of the DLC powder 100 on the inner wall of the crucible 16. It is considered that the simultaneous occurrence of the two processes produces the DLC powder.
  • magnetic field forming power is supplied to the electromagnetic coils 28 and 30. This causes the above-mentioned mirror magnetic field to be formed, which confine the plasma 200 within the crucible 16. As a result, the density of the plasma 200 increases, which further increases the production rate of the DLC powder on the inner wall of the crucible 16.
  • DC power Ea is supplied to the gas introducing pipe 22 from the nozzle power supply 26, which makes the gas introducing pipe 22 serve as a second anode electrode. Electrons in the plasma 200 are drawn into the gas introducing pipe 22 serving as the second anode electrode. As a result, a high-density discharge, i.e. so-called hollow-anode discharge 300, is generated around the gas introducing pipe 22, and around the tip end of the gas introducing pipe 22 in particular.
  • the hollow-anode discharge 300 increases the acetylene gas decomposition efficiency, which leads to further improvement of the production rate of the DLC powder 100 on the inner wall of the crucible 16.
  • the functioning of the gas introducing pipe 22 as a second anode electrode can stabilize the plasma 200.
  • the plasma 200 is generated by the application of the asymmetrical pulse power Ep to the vacuum tank 12 acting as an anode electrode and to the crucible 16 acting as a cathode electrode.
  • the DLC powder 100 produced by the use of the plasma 200 is deposited not only on the inner wall (surface) of the crucible 16 but also on the inner wall (surface) of the vacuum tank 12.
  • the performance as the anode electrode of the vacuum tank 12 is degraded, resulting in instability of the plasma 200.
  • the gas introducing pipe 22 functioning as the second anode electrode as described above or, in other words, since the gas introducing pipe 22 functions also as the electrode for generating the plasma 200, the generation of the plasma 200 is sustained, and the plasma 200 is stabilized.
  • the stabilization of the plasma 200 makes it possible to produce the DLC powder 100 for a long time, which means mass production of the DLC powder 100 is available, leading to mass production of OLC, the ultimate product.
  • the heater 20 is supplied with heating electric power so that the heater 20 becomes heated, whereby the temperature of the inner wall of the crucible 16 and, thus, the temperature at which the DLC powder 100 is produced, are controlled. It should be noted that, when the temperature at which the DLC powder 100 is produced is too high, the hydrogen radicals and the hydrogen ions, which are particles resulting from the decomposition of the acetylene gas by the plasma 200, react with the DLC powder 100 to gasify the DLC powder 100. This may lower the rate of production of the DLC powder 100.
  • Figure 3 shows relationship between the temperature and the rate, at which the DLC powder 100 is produced.
  • the relationship shown in Figure 3 is the result of actual measurements, under the condition that the flow rate of the argon gas was 50 ml/min., the flow rate of the acetylene gas was 300 ml/min., the pressure P in the vacuum tank 12 was 3 Pa, the frequency of the asymmetrical pulse power Ep was 100 KHz, the duty ratio of the asymmetrical pulse power Ep was 30 %, the average voltage value of the asymmetrical pulse power Ep was -500 V, the voltage value Va of the DC power Ea was +30 V, and the magnetic field in the crucible 16 was 5 mT.
  • the DLC powder producing rate is about 8 g/h when the DLC powder producing temperature is about 300 °C or lower, and such rate may be a rate which enables mass production.
  • the rate of producing the DLC powder 100 abruptly decreases greatly.
  • the DLC powder producing temperature is 700 °C
  • the DLC powder producing rate is 3.4 g/h, which is less than half the rate available when the temperature is lower than 300 °C.
  • the temperature at which the DLC powder 100 is to be produced be controlled to a temperature equal to or lower than 300 °C, preferably to a temperature in a range of from 100 °C to 300 °C.
  • the second, DLC-to-OLC converting processing step is carried out. Specifically, the supply of the magnetic field forming power to the magnetic coils 28 and 30 is stopped. At the same time, the supply of the DC power Ea to the gas introducing pipe 22 and the supply of the asymmetrical pulse power Ep to the crucible 16 are also stopped. Further, the introduction of argon and acetylene gasses into the vacuum tank 12 through the gas introducing pipe 22 is stopped. The supply of the heater energizing power to the heater 20 may or may not be stopped. After that, the vacuum tank 12 is evacuated anew.
  • argon gas only is introduced through the gas introducing pipe 22 into the vacuum tank 12.
  • the introduced argon gas changes the interior of the vacuum tank 12 to an argon gas atmosphere.
  • the pressure P within the vacuum tank 12 is 10 Pa, for example.
  • the heater 20 is used to heat the inner wall of the crucible 16 to 1,600 °C. This causes the DLC powder 100 in the crucible 16 to be converted to OLC.
  • the DLC-to-OLC converting processing is continued for 30 minutes, for example.
  • a post-treatment for taking the finished OLC out of the vacuum tank 12 is carried out.
  • the following post-treatment is done.
  • the supply of the heater energizing power to the heater 20 is stopped, and at the same time, the supply of argon gas to the vacuum tank 12 through the gas introducing pipe 22 is stopped.
  • the pressure P in the vacuum tank 12 is gradually returned to a level almost the same as the atmospheric pressure.
  • the interior of the vacuum tank 12 is opened to the air.
  • the crucible 16 with the finished OLC therein are taken out of the vacuum tank 12. This completes a series of post-treatment processing and, accordingly, the OLC producing processing including the post-treatment.
  • the OLC in the taken-out crucible 16 is collected by means of proper collecting means, e.g. a brush.
  • Figure 4 is a picture of the thus manufactured OLC taken by observing it through a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • Figure 4 what are encircled with white broken lines are OLC.
  • OLC is present.
  • the OLC shown in Figure 4 was manufactured from the preceding material, i.e. the DLC powder 100 which was produced, with the DLC powder producing temperature of 200 °C employed (in the first step, i.e. the DLC producing processing) and with the same conditions as described with reference to Figure 3 employed.
  • the DLC powder 100 i.e. the preceding material for OLC, too, was observed through a transmission electron microscope, and a picture as shown in Figure 5 was obtained.
  • Figure 5 it is seen that OLC is present in portions encircled with white broken lines.
  • OLC is formed, though it is only in a small amount, in the DLC powder 100.
  • the DLC power 100 can be securely converted to OLC by heating the DLC powder 100 at 1,600 °C (in other words, by carrying out the second step, DLC-to-OLC converting processing).
  • a solid line curve L1 represents the result of analysis of the OLC manufactured in accordance with the present invention.
  • the other curves L2 through L5 represent the results of analysis of controls.
  • the dash and dot line curve L2 represents the result of analysis of OLC obtained by heating the DLC powder 100 at 1,000 °C in the second step, DLC-to-OLC converting processing, and the two dots and dash line curve L3 represents the result of analysis of the DLC powder 100, which is the preceding material.
  • the broken line L4 represents the result of analysis of DNP used as the starting material in the aforementioned prior technology.
  • the dot line curve L5 represents the result of analysis of OLC manufactured by heating the DNP at 1,600 °C in the prior technology.
  • a solid line curve L11 represents the result of analysis of the OLC manufactured in accordance with the described embodiment.
  • the other curves L12 and L13 represent the results of analysis of comparison materials.
  • the dot and dash line curve L12 shows the result of analysis of the OLC obtained by heating the DLC powder 100 at 1,000 °C in the second, DLC-to-OLC conversion processing step
  • the dot line curve L13 shows the result of analysis of the OLC prepared by heating DNP at 1,600 °C in accordance with the prior technology.
  • OLC can be manufactured, using acetylene gas as the starting material.
  • Acetylene gas is much inexpensive than DNP used as the starting material in the above-described prior technology. Accordingly, the described embodiment of the present invention can provide OLC at a significantly lower cost than the prior technology.
  • Acetylene gas is used in the described embodiment as the starting material, but the present invention is not limited to it.
  • Other hydrocarbon gas e.g. methane gas, ethylene gas and benzene gas, may be used.
  • a hydrocarbon gas obtained through gasification of alcohol may be employed instead. It has been found by experiments, however, that, when methane gas is used, the rate of producing DLC powder 100 is lower than when acetylene gas is used, or, more specifically, the DLC powder producing rate when methane gas is used is about one-fifth of the rate when acetylene gas is used. It is the same in the case of using ethylene gas.
  • benzene gas In case of benzene gas, it is necessary to gasify benzene since it is liquid, and therefore an extra cost including a cost for providing gasifying equipment is necessary. In addition, there is a possibility that benzene gas will re-liquefy in the vacuum pump, which may lower the exhaustion efficiency of the vacuum pump. Moreover, benzene gas is toxic and carcinogenic, and therefore the use of benzene gas is harmful. Since alcohol is also liquid, the use of alcohol requires additional costs including a cost for providing gasifying equipment. Considering these factors together, acetylene gas is the most preferable starting material in view of the rate of producing DLC powder 100, the cost, easiness of handling, easiness of procurement, safety etc.
  • sine-wave, high-frequency power having a frequency of 13.56 MHz may be used as the discharging power in the first step, or the DLC powder producing processing.
  • AC power it is important to use AC power as the discharging power in order to prevent charge-up.
  • the asymmetric pulse power Ep has its frequency, duty ratio and average voltage value Vp adjustable, and therefore has greater flexibility than high-frequency power to deal with various situations.
  • the asymmetric pulse power Ep is more preferable to the high-frequency power as the discharging power.
  • a self-discharge excitation (which is also called “cold-cathode type excitation) is employed to excite the plasma 200, but other exciting techniques, for example, high-frequency plasma CVD, microwave plasma CVD, and ECR (Electron Cyclotron Resonance) plasma CVD, hot-cathode PIG (Penning Ionization Gauge) plasma CVD, may be used, instead.
  • other exciting techniques for example, high-frequency plasma CVD, microwave plasma CVD, and ECR (Electron Cyclotron Resonance) plasma CVD, hot-cathode PIG (Penning Ionization Gauge) plasma CVD, may be used, instead.
  • a so-called heater heating technique in which the heater 20 is used to heat the DLC powder 100 in the second step, DLC-to-OLC conversion processing step, but other techniques, e.g. infrared lamp heating, radio-frequency induction heating, electron beam radiation heating, and plasma heating, may be used instead.
  • experiments conducted have confirmed that the DLC powder 100 can be converted to OLC by employing a heating temperature of at least 700 °C or above.
  • the interior of the vacuum tank 12 is an argon gas atmosphere, but the atmosphere is not limited to it.
  • an atmosphere of other inert gas e.g. neon (Ne) gas and xenon (Xe) gas
  • the DLC-to-OLC conversion may be carried out in a vacuum rather than in an inert gas atmosphere.
  • an inert gas e.g. neon gas and xenon gas
  • the discharging gas in place of argon gas.
  • the first-step DLC powder producing processing and the second-step DLC-to-OLC conversion processing may be carried out in separate apparatuses.
  • an apparatus for carrying out the DLC powder producing processing and an apparatus for carrying out the DLC-to-OLC conversion processing may be provided separately, and the DLC powder 100 produced in the DLC powder producing processing apparatus is transferred to the DLC-to-OLC conversion processing apparatus where the DLC powder 100 is converted to OLC.
  • the DLC powder producing processing and the DLC-to-OLC conversion processing may be successively carried out in so-called in-line system.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Electromagnetism (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical Vapour Deposition (AREA)
  • Carbon And Carbon Compounds (AREA)
EP11867256.7A 2011-06-06 2011-06-06 Method for producing onion-like carbon Not-in-force EP2573047B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2011/062923 WO2012168993A1 (ja) 2011-06-06 2011-06-06 オニオンライクカーボンの作製方法

Publications (3)

Publication Number Publication Date
EP2573047A1 EP2573047A1 (en) 2013-03-27
EP2573047A4 EP2573047A4 (en) 2015-04-15
EP2573047B1 true EP2573047B1 (en) 2018-10-31

Family

ID=47295600

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11867256.7A Not-in-force EP2573047B1 (en) 2011-06-06 2011-06-06 Method for producing onion-like carbon

Country Status (7)

Country Link
US (1) US8992880B2 (ja)
EP (1) EP2573047B1 (ja)
JP (1) JP5159960B2 (ja)
KR (1) KR101373640B1 (ja)
CN (1) CN102933490B (ja)
TW (1) TWI457275B (ja)
WO (1) WO2012168993A1 (ja)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104209062B (zh) * 2013-05-20 2016-07-06 燕山大学 超高硬度纳米孪晶金刚石块体材料及其制备方法
US10160654B2 (en) 2014-11-13 2018-12-25 Yanshan University Ultrahard nanotwinned diamond bulk material and method for preparing the same
US10428197B2 (en) 2017-03-16 2019-10-01 Lyten, Inc. Carbon and elastomer integration
US10920035B2 (en) 2017-03-16 2021-02-16 Lyten, Inc. Tuning deformation hysteresis in tires using graphene
US9862606B1 (en) 2017-03-27 2018-01-09 Lyten, Inc. Carbon allotropes
CN109112330B (zh) * 2018-08-20 2020-10-16 东南大学 一种纳米洋葱碳增强钛基复合材料及其制备方法
CN109207835A (zh) * 2018-10-12 2019-01-15 燕山大学 一种Fe基宽应用温度自润滑复合材料及其制备方法
CN109321849B (zh) * 2018-10-12 2021-04-02 燕山大学 一种适用于高低温的Fe基自润滑复合材料及其制备方法
WO2021040931A1 (en) 2019-08-29 2021-03-04 Novonix Battery Testing Services Inc. Lithium transition metal oxide and precursor particulates and methods
US11309545B2 (en) 2019-10-25 2022-04-19 Lyten, Inc. Carbonaceous materials for lithium-sulfur batteries
US11398622B2 (en) 2019-10-25 2022-07-26 Lyten, Inc. Protective layer including tin fluoride disposed on a lithium anode in a lithium-sulfur battery
US11489161B2 (en) 2019-10-25 2022-11-01 Lyten, Inc. Powdered materials including carbonaceous structures for lithium-sulfur battery cathodes
US11342561B2 (en) 2019-10-25 2022-05-24 Lyten, Inc. Protective polymeric lattices for lithium anodes in lithium-sulfur batteries

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR900008505B1 (ko) * 1987-02-24 1990-11-24 세미콘덕터 에너지 라보라터리 캄파니 리미티드 탄소 석출을 위한 마이크로파 강화 cvd 방법
JPH11157818A (ja) 1997-11-21 1999-06-15 Masanori Yoshikawa オニオングラファイト作製方法およびそのグラファイト製品
JP2000109310A (ja) 1998-08-03 2000-04-18 Osaka Gas Co Ltd 機能性炭素材料の製法
WO2000078674A1 (de) 1999-06-18 2000-12-28 Carbo-Tec Gesellschaft Für Nano-Und Biotechnische Produkte Mbh Verfahren zur dynamisch-chemischen herstellung von diamantartigen kohlenstoffstrukturen, diamantartige kohlenstoffstrukturen und verwendungen von diamantartigen kohlenstoffstrukturen
CN1207188C (zh) * 2003-10-10 2005-06-22 太原理工大学 洋葱状富勒烯的cvd制备方法
JP4680612B2 (ja) * 2005-01-24 2011-05-11 株式会社不二越 カーボンオニオンの製造方法
JP5298309B2 (ja) * 2007-02-17 2013-09-25 国立大学法人東京工業大学 カーボンオニオンおよびその製造方法、ならびに、ゲル組成物およびその製造方法
JP5375197B2 (ja) * 2009-02-28 2013-12-25 伸夫 大前 オニオンライクカーボンの作製方法
WO2011004609A1 (ja) 2009-07-08 2011-01-13 Ohmae Nobuo Ｃｏ２リサイクリング方法、ｃｏ２削減方法、および装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
KR101373640B1 (ko) 2014-03-12
EP2573047A4 (en) 2015-04-15
TW201249741A (en) 2012-12-16
EP2573047A1 (en) 2013-03-27
KR20130029762A (ko) 2013-03-25
JP5159960B2 (ja) 2013-03-13
TWI457275B (zh) 2014-10-21
CN102933490B (zh) 2015-02-11
WO2012168993A1 (ja) 2012-12-13
US8992880B2 (en) 2015-03-31
JPWO2012168993A1 (ja) 2015-02-23
CN102933490A (zh) 2013-02-13
US20130189178A1 (en) 2013-07-25

Similar Documents

Publication Publication Date Title
EP2573047B1 (en) Method for producing onion-like carbon
US11673807B2 (en) Carbon nanostructured materials and methods for forming carbon nanostructured materials
JP4963539B2 (ja) カーボンナノチューブの作製方法及びその方法を実施するプラズマｃｖｄ装置
US20020102353A1 (en) Method of producing a nanotube layer on a substrate
JP2008056546A (ja) 炭素構造体の製造装置及び製造方法
JP5052954B2 (ja) Ｃｎｔ成長方法
JP2541434B2 (ja) カ―ボンナノチュ―ブの製造方法
Ayesh et al. Mechanisms of Ti nanocluster formation by inert gas condensation
JP3837451B2 (ja) カーボンナノチューブの作製方法
JPWO2011025000A1 (ja) 配向カーボンナノチューブの製造方法
JP4919272B2 (ja) カーボンナノチューブ形成装置、カーボンナノチューブ形成方法
JP3837556B2 (ja) カーボンナノチューブを備えた金属ワイヤー又はキャピラリー及びカーボンナノチューブの形成方法
JP5213099B2 (ja) カーボンファイバーシート上のカーボンナノチューブの成長方法およびカーボンナノチューブエミッター
JP2001192829A (ja) カーボンナノチューブ薄膜形成ｅｃｒプラズマｃｖｄ装置及び該薄膜の形成方法
WO2023218990A1 (ja) 成膜装置及び成膜方法
JP4448586B2 (ja) 大口径カーボンナノチューブ薄膜形成プラズマｃｖｄ装置及び該薄膜の形成方法
JP2010174378A (ja) 薄膜形成方法
JPWO2005054127A1 (ja) 誘導フラーレンの製造装置及び製造方法
JP5968136B2 (ja) Ｄｌｃ粉末作製装置および方法
Sarangi et al. Carbon nanotubes grown on metallic wires by cold plasma technique
JP2006057122A (ja) プラズマ化学気相堆積装置及びプラズマ化学気相堆積方法
Hiramatsu et al. Preparation Methods
JP2004018350A (ja) カーボンナノチューブの製造方法
JP2017031001A (ja) ダイヤモンドライクカーボン粉末およびその作製方法
JP2006089359A (ja) ナノ構造材料製造装置及び製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20121219

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
RA4 Supplementary search report drawn up and despatched (corrected)

Effective date: 20150312

RIC1 Information provided on ipc code assigned before grant

Ipc: C01B 31/02 20060101AFI20150306BHEP

Ipc: B82Y 40/00 20110101ALI20150306BHEP

Ipc: B82Y 30/00 20110101ALI20150306BHEP

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20170828

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602011053524

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C01B0031020000

Ipc: B82Y0030000000

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: B82Y 40/00 20110101ALI20180511BHEP

Ipc: C01B 32/18 20170101ALI20180511BHEP

Ipc: B82Y 30/00 20110101AFI20180511BHEP

INTG Intention to grant announced

Effective date: 20180612

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1059145

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181115

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602011053524

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20181031

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1059145

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190131

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190228

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190301

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190201

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20190521

Year of fee payment: 9

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602011053524

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20190510

Year of fee payment: 9

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20190801

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20190605

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20190630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190606

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190630

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190630

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190630

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190606

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602011053524

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20200606

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200630

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200606

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20110606

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181031